KR940003875B1 - Noninflammable polyester - Google Patents

Abstract

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Description

Flame retardant polyester

The present invention relates to a flame retardant polyester, and more particularly, to a flame retardant polyester having excellent flame retardant performance while using a compound which is cheaper and has a smaller amount of content than conventional methods. Existing methods for imparting flame retardancy to linear polyesters include: (1) adding a refractory material for copolymerization or blending to produce a polyester polymer; and (2) applying a flame retardant material to the linear polyester during manufacture of a molded article (or yarn). A method of mixing or a method of imparting flame retardancy by post-processing a linear polyester molded article (or fabric) has been proposed.

However, in all these methods, since expensive flame retardants are used, there is a problem in that the cost of the product increases, and according to the kind of flame retardants added, the compatibility with polyester is poor. In the case of adding and copolymerizing, there is a problem that side reactions and decomposition occur in the copolymerization reaction and the like. On the other hand, in the case of post-processing a flame retardant material to the polyester, there is a problem in sustainability because the treated flame retardant is attached only to the surface of the polyester, and also the appearance, texture, etc. of the product may be damaged due to the surface adhesion. There is also.

Accordingly, the present inventors use a predetermined compound which is industrially inexpensive and capable of copolymerization without fear of side reactions and decomposition during copolymerization with polyester, and adds it at a predetermined ratio in preparing a polyester polymer. Recognizing that the above-mentioned problems can be solved by copolymerization, and many studies have been conducted. As a result, using a phosphorus compound having the following general formula (I) as a copolymer and adding a predetermined amount during the polymerization of polyester, Linear polyesters are provided in much the same way as when polymerizing the polyesters, and the flame retardancy and the sacrificial properties of these polyesters were also found to complete the present invention.

(Wherein X is 0 or 1, and R ¹ and R ² are the same or different groups, each being a hydrogen atom, an alkyl group having 10 or less carbon atoms, or —CH ₂ CH ₂ OH).

Accordingly, an object of the present invention is to provide a flame retardant polyester having excellent flame retardant performance while using a compound which is cheaper and has a smaller amount of inclusion than a conventional method.

In order to achieve the object mentioned above, this invention mixes and copolymerizes the phosphorus compound represented by following General formula (I) at the time of polyester superposition | polymerization, and contains 2-10 mol% of phosphorus atoms in a final polyester polymer. It provides the flame-retardant polyester characterized by containing.

(Wherein X is 0 or 1, and R ¹ and R ² are the same or different groups, each being a hydrogen atom, an alkyl group having 10 or less carbon atoms, or —CH ₂ CH ₂ OH).

The compound of formula (I) described above may be prepared by heating bis- (2-chloroethyl) hydrogen phosphite and an unsaturated diester compound in an ethylene glycol solvent. Can be. As said unsaturated diester compound, maleic acid, itaconic acid, lower alkyl ester, an acid anhydride, etc. can be used.

The method for preparing a phosphorus compound as described above will be described in more detail with an example of using bis- (2-chloroethyl) hydrogen phosphite and itaconic acid as starting materials.

The molar ratios of bis- (2-chloroethyl) hydrogen phosphite, itaconic acid and ethylene glycol are mixed at 1: 1: 1 to 4, respectively, and the reaction temperature is 130 to 190 占 폚, more preferably 160 under an inert gas atmosphere. The target compound containing the target general formula (I) can be manufactured by making it heat-stirring at -170 degreeC and making it react for 1-3 hours. At this time, it is more preferable to add sodium alkoxide such as sodium ethoxide as a catalyst for promoting the reaction.

Specific examples of the phosphorus compound represented by the general formula (I) include the following compounds.

When a flame retardant polyester is prepared by adding a phosphorus compound as described above, the phosphorus (P) atoms in these phosphorus compounds interact with each other to contain a smaller amount of personnel than conventional methods. Even if it is made, much better flame retardant performance can be obtained.

In the present invention, the content of the number of persons in the final polyester polymer is set to 2 to 10 mol%, more preferably 3 to 5 mol%. When the amount of the phosphorus-containing compound is too small, the content of the number of phosphorus in the final polyester becomes less than 2 mol%, it is difficult to achieve the desired flame retardant performance, and when the content of the phosphorus exceeds 10 mol%, When the flame retardant performance becomes difficult to be achieved, and the content of the personnel exceeds 10 mol%, the flame retardant performance is improved, but the physical properties of the flame retardant polyester obtained are not only deteriorated but also adversely affect the operability. On the other hand, among the compounds mentioned above (I-1), (I-5), (I-6) is preferably copolymerized by adding the initial reaction of the general TPA method, the other compounds are transesterified by the DMT method It is preferable to add before the reaction or to copolymerize it in the pre-condensation step.

In this way, it is possible to obtain a flame retardant polyester having excellent flame retardant performance while adding a compound which is much cheaper than the conventional method and contains a small amount of containing compound in a very simple method.

Next, examples of the flame retardant polyesters of the present invention will be described to further describe the present invention. In the following examples, the intrinsic viscosity of the polymer was measured at 30 ° C. in a phenol and 1,1,2,2-tetrachloroethane mixed solvent (3: 2), and the content of trivalent phosphorus in isopropyl alcohol It dissolved and measured by the iodine method.

On the other hand, in the fire resistance test, the yarn obtained by spinning and stretching the obtained polyester polymer by a conventional method was knitted into a Meriya's knitted fabric, 1 g of this knitted fabric was cut into 10 cm lengths, inserted into a 10 mm thick immersion coil, and then 45 deg. Ignite at the bottom with the angle of ignition at the bottom and then remove the fire source and repeat the ignition again when the light is turned off.The number of ignition required for complete combustion of one sample is measured for each of the five samples. Evaluated as.

[Production example of flame retardant]

206 kg of bis- (2-chloroethyl) hydrogen phosphite, 130 kg of itaconic acid and 170 L of ethylene glycol were taken into a reaction vessel, mixed, stirred for 5 minutes, and heated slowly to 160 ° C. over 30 minutes to raise the temperature. At 160 ° C. for 2 hours, the byproduct water was condensed, and an excess of ethylene glycol was removed by applying a vacuum when the amount of water did not change for 1 to 2 minutes. This gave 420 kg (98%) of crude product. Other flame retardants can also be prepared by the same method as described above.

Example 1

248 kg of ethylene glycol (EG) was mixed with 388 kg of dimethyl terephthalate, and 0.03% by weight of zinc acetate and 0.03% by weight of antimony oxide (Sb ₂ O ₂ ) were further added to the dimethylterephthalate, and then the mixture was added. Compound (I-3) containing 34 kg (4 mol%) containing a transesterification reaction by heating at 150-230 ° C. for 120 minutes.

After further adding, the temperature and pressure were adjusted to be 275 ° C. and 0.2 mmHg over 1 hour, and then further reacted for 1 hour and 30 minutes under these conditions to obtain the polyester polymer of the present invention. The intrinsic viscosity of the obtained polymer was 0.607, the melting point was 246 ° C, and the phosphorus residual ratio in the polymer was 98%.

The polymer obtained by spinning at 285 ° C. using an extruder type spinning machine according to a conventional method is stretched 3.5 times on a hot plate of 87 ° C. according to a conventional method to have strength of 4.5 g / d and elongation. Obtained a drawing yarn of 35%. The flame retardance of the knitted fabric of this fiber was measured and the results are shown in the following table.

Example 2

32.9 kg (4 mol%) of phosphorus compound (I-9)

A polyester polymer of the present invention was obtained in the same manner as in Example 1 except that was added. The inherent viscosity of the obtained polymer was 0.581, the melting point was 244 ° C, and the phosphorus residual ratio in the polymer was 99%.

The polymer was spun and stretched in the same manner as in Example 1, then fabricated into a knitted fabric to measure flame retardancy, and the results are shown in the following table.

EXAMPLES 3-9

Instead of 34 kg (4 mol%) of phosphorus compound (I-3), the above phosphorus compounds (I-1), (I-2), (I-4), (I-5), (I-6) The polyester polymer of the present invention was obtained in the same manner as in Example 1 except that 4 mol% of (I-7) and (I-8) were each added. Intrinsic viscosity, melting | fusing point, the residual ratio in a polymer, etc. of the obtained polymer were measured and shown in the following table.

In addition, using these polymers, spinning and stretching in the same manner as in Example 1, and then produced into a knitted fabric to measure the flame retardancy is shown in the following table.

Comparative Examples 1 to 4

The treatment was carried out in the same manner as in Example 1, except that the amount of the compound (I-3) containing the phosphorus compound (I-3) used in Example 1 was changed to 0.1 mol%, 0.5 mol%, 1 mol%, and 15 mol%. The polyester polymer of the example was prepared. Intrinsic viscosity, melting | fusing point, the residual ratio in a polymer, etc. of the obtained polymer were measured and shown in the following table.

In addition, using these polymers, spinning and stretching in the same manner as in Example 1, and then produced into a knitted fabric to measure the flame retardancy is shown in the following table.

TABLE 1

As confirmed by the results of Table 1, the polyesters of the present invention all exhibit excellent flame retardant effects.

On the other hand, in the case of the comparative example in which the addition amount of the phosphorus compound exceeds the scope of the present invention, the flame retardant performance was very poor, especially when the addition amount was 15 mol%, gelation occurred during the polymerization reaction, and thus the desired polyester polymer was used. Couldn't get it.

Claims (2)

The flame-retardant polyester characterized by mixing and copolymerizing the phosphorus compound represented by following General formula (I) at the time of polyester polymerization, and containing 2-10 mol% of phosphorus atoms in the final polyester polymer. (Wherein X is 0 or 1, and R ¹ and R ² are the same or different groups, each being a hydrogen atom, an alkyl group having 10 or less carbon atoms, or —CH ₂ CH ₂ OH). The flame retardant polyester according to claim 1, wherein the phosphorus content in the final polyester polymer is 3 to 5 mol%.